Condensation product of the benzo-pyrene-quinone series and process of preparing the same



Patented Jan. 7, 1930 UNITED STATES PATENT OFFICE GEORG KRANZLEIN AND HEINRICH VOLLHANN, OF HOCHST-OIT-THE- MAIN, GERMANY,

ASSIGNORS TO GENERAL ANILINE WORKS, INC 01 NEW YORK, N, Y., A CQRPORA- TION OI DELAWARE CONDENSATION PRODUCT OF THE IBENZO-PYRENE-QUINONE SERIES PREPARING THE SAME mp raocnss or No Drawing. Application filed May 7, 1926, Serial 1T0. 107,485, and in Germany Kay 11, 1925.

This invention relates to a process of preparing condensation products of the anthraquinone series and to the products produced thereby. More specifically the invention relates to the production of products of the benzo-pyrene-quinone series.

German Patent 412,053 describes the production of dibenzo-pyrene-quinone dyestufis by the action of aromatic acidhalogenides on benzanthrones. The mechanism of the reaction is explained as consisting of a closing of the ring following the formation of aroylbenzanthrones. This supposition was confirmed in Germain patent specification No. 420,412 according to which the aroylbenzanthrones were converted into dibenzo-pyrene-quinones by means of aluminium chloride condensation.

. It has now been found that in a surprising way the aroylbenzanthrones of the general formula wherein each R stands for hydrogen or both Rs together stand for the bivalent radical H CCH on alkaline condensation yield produced on alkaline condensation, but dyestufis of the violanthrene series, the aroyl residue being split off.

The ring-closing of the aroylbenzanthrones of the general formula given above by alkalinecondensation,whichleadstotheformation of bodies of the benzo-pyrene-quinone series extremely smoothly, is of great commercial importance since in this manner bodies of the benzo-pyrene-quinone class are made accessible, which heretofore have-not been capable of production at all. An example is benzo-naphtho-pyrene-quinone, which results by the fusion of a-naphthoylbenzanthrone with potassium'hydroxide.

The invention is illustrated by the followin examples but it is to be understood that t e invention is not limited to the specific products mentioned in these examples.

1. 1 part by weight of bz-l-a-naphtho lbenzanthrone is stirred with 4 parts y weight of powdered potassium hydroxide and 3 parts by volume of alcohol. It is heated next for a quarter of an hour at 100 C., whereupon a green melt is obtained. Then the temperature is raised for a short time up to 230 C. with vaporization of the alcohol. After it has cooled down, the mass is diluted with hot water, the dyestuif formed is vatted by the addition of hydrosulfite and the vat is sucked off. The dyestuff is obtained by blowing out with air in the form of pure orange-brown flakes. The color of its solution in concentrated sulfuric acid is clear dark blue. Its vat is carmine-red with a strong brown-orange colored bloom and dyes cotton brown-orange after ageing.

The benz l-a-na hthoylbenzanthrone can be obtained by con ensing bz-l-benzanthroncarboxylic acid chloride andnaphthalene by V means of aluminium chloride. Frompyridine it or stallizes as a bright yellow substance me ting at fi l-245. The-color of its solution in concentrated sulfuric acid is cherry red.

2. 1 part by weight of 4-acenaphthyl-bzl-ben'zanthronyl ketone is rubbed with alcohol to a thick paste and this is introduced into 5 partsby weight of fusedpotassium hydroxide at about 150 C. The temperature is gradually raised up to 230 C. The working up1 is carried out as described in Example 1. T e resulting dyestufi possesses the following constitution:

Its own color and its dyeing on cotton is rust-brown. The vat is bluish-red. The.

droxide an aroylbenzanthrone .of the general formula:

wherein each stands for hydrogen or both Rs together stand for the bivalent radical H2C CH2.

2. The process of preparing condensation products of the benzo-pyrene-quinone series which comprises heating with potassium hydroxide to a temperature above about 100 C.

an aroylbenzanthrone of the general formula: m

wherein each R stands for hydrogen or both Rs together 'stand for the bivalent radical 3. T e process of preparing condensation products of the benzo-pyrene-quinone series which comprises heating with potassium hydroxide to a temperature between about LOO-230 C. an aroylbenzanthrone of the general formulaz' whereineach R stands for hydrogen or both Q .Rs together stand 'for the H,lC-GH ivalent radical 4. The process of pre aring benzo-naphtho-.pyrene-quinone whic B2-1=a-naphthoylbenzanthronewith potassium hydroxide. 1

comprises fuslng' 5. The process of preparing benzo-naphtho-pyrene-quinone which comprises heat- 111g Bz-l-a-naphthoylbenzanthrone with potassium hydroxide to a temperature above about 100 C".

6. The process of preparing benzo-naphthoyrene-quinone which comprises heatmg z-l-u-naphthoylbenzanthrone with potassium hydroxide to a temperature between v about 100230 o.

7 As new products the condensation products of the benzo-pyreneuinone series having probably the general ormula:

v 8 wherein the Xs stand for hydrogen atoms or stand for CH groups which are linked together by a single bond, which products are in a, dry state orange-brown to rustbrown powders, soluble in concentrated sulfuric acid with a blue color, and dye cotton from a carmine-red to a bluish-red vat orange-brown to rust-brown shades.

8. As a new product the benzo-naphthopyrene-quinone of the following formula:

which product is in the dry state an orangebrown powder, soluble in concentrated sulfuric acid with a dark blue color and dyes cotton from a carmine-red vat orange-brown shades.

In testimony whereof, we aflix our signatures.

GEORG KRANZLEIN. HEINRICH VOLLMANN. 

